8-Exo-hydroxymethyl-endo-tricyclo [5.2.1.02,6 ]decane

ABSTRACT

8-EXO-HYDROXYMETHYL-ENDO-TRICYCLO [5.2.1.0 2 ,6 ] DECANE IS PREPARED BY HYDROGENATING 8- AND 9-EXO-FORMYL-ENDO-TRICYCLO [5.2.1.0 2 ,6 ] DECA-3-ENES.

FIELD OF THE INVENTION

The present invention relates to 8-exo-hydroxymethyl-endo-tricyclo[5.2.1.0²,6 ] decane.

Further, the present invention relates to a process for preparing8-exo-hydroxymethyl-endo-tricyclo [5.2.1.0²,6 ] decane of formula (I):##STR1## characterized by hydrogenating 8- and9-exo-formyl-endo-tricyclo [5.2.1.0²,6 ] deca-3-enes of formula (II):##STR2## in the presence of platinum oxide, Raney nickel or the like ascatalyst under elevated hydrogen pressure.

SUMMARY OF THE INVENTION

From 8-exo-hydroxymethyl-endo-tricyclo [5.2.1.0²,6 ]-decane of formula(I), 4-homoisotwistane (tricyclo [5.3.1.0³,8 ]-undecane (III)) can bederived at a high selectivity by hydride transfer reductionrearrangement: ##STR3##

It has been revealed already by the inventors that various derivativesderived from the compound of formula (III) exhibit various physiologicaleffects such as typical antiviral effects and they can be used for manyuseful purposes, for example, in Japanese Patent Application No.93968/1975. The compound of formula (I) obtained by the invention isvery important starting material for the synthesis of those usefulcompounds.

The catalyst of the present invention is one of those used forhydrogenation of olefins and aldehydes, such as compounds of platinum,palladium, nickel, cobalt, iron, copper, for example, platinum oxide,Raney nickel or the like.

In carrying out the process of the present invention, the catalyst isused in a weight ratio of the catalyst to starting material (II) ofhigher than 1/100,000 to 1/1; weight ratio of from 1/1,000 to 1/10 ispreferred for attaining a suitable reaction velocity.

A solvent is not necessarily used, but a lower alcohol of C₁ to C₄ suchas methanol, ethanol, n-propanol or i-propanol or an ether solvent suchas diethyl ether or tetrahydrofuran may be used.

The reaction temperature ranges from room temperature to +200° C,preferably 30°-150° C. The first step of the reaction can be carried outat room temperature without necessitating any special heating, since itis hydrogenation in the 3(4) position of the olefinic starting materialof formula (II). Then, hydrogenation reaction of the aldehyde is carriedout under heating at a temperature preferably in the range of from +30°C to +200° C, more preferably 50°-150° C. The hydrogen pressure is inthe range of 10-200 atms., preferably 50-100 atms.

The starting material of formula (II) of the present invention can besynthesized, for example, by oxo reaction of endo-tricyclo [5.2.1.0²,6 ]deca-3,8-diene in the presence of a rhodium triaryl phosphine catalyst.The structure thereof has been proved by the inventors.

EXAMPLE

149.6 Grams (0.9 mole) of 8- and 9-exo-formyl-endo-tricyclo [5.2.1.0²,6] deca-3-ene, 100 ml. of methanol and 200 mg of platinum oxide arecharged in a pressure vessel. Air in the vessel is replaced withhydrogen. The mixture is stirred at room temperature under a hydrogenpressure of 90 atms. After hydrogen absorption ceases, the reactiontemperature is raised to 120° C and hydrogenation is continued furtheruntil hydrogen absorption ceases again. After completion of thereaction, the catalyst is filtered out and the filtrate is distilled outunder reduced pressure to obtain a colorless, viscous oily product.

Boiling point: 95°-96° C/0.3 mmHg, D²⁸ =1.5129

Elementary analysis: Found: C 79.2; H 10.5%. Theoretical (as C₁₁ H₁₈ O):C 79.5; H 10.9%.

IR (liquid film, cm⁻¹) 3600-3100(O-H), 1470, 1450, 1020(C-O).

NMR (CCl₄ solvent, TMS internal standard, δ). 4.3(OH), 3.3(CH₂ O, d,J═7Hz), 2.5-0.9(15H, complex multiplet).

MS 166(1.9 M⁺), 148(13), 135(100), 107(13), 93(16), 91(13), 81(19),80(22), 79(28), 67(47), 41(12).

REFERENTIAL EXAMPLE

66 Grams (0.5 mole) of endo-tricyclo [5.2.1.0²,6 ]3,8-diene, 100 ml. ofbenzene, 345 mg (0.0005 mole) of [RhCl(CO) (PPh₃)₂ ] and 0.25 ml. oftriethylamine are charged in an autoclave. Air in the autoclave isreplaced with carbon monoxide gas and 100 atms. of a mixture of carbonmonoxide and hydrogen (1:1 molar ratio) are added thereto. Reactiontemperature is kept at 70° C under stirring and reaction is effectedtill 1.2 equivalents of the gas are absorbed. After completion of thereaction, the vessel is cooled and the reaction mixture is taken out.After removing the solvent, the product is subjected to distillation toobtain 8- and 9-exo-formyl-endo-tricyclo [5.2.1.0²,6 ] undeca-3-ene(66.4 g; yield 82%) as colorless oily product.

Boiling point: 77° C/0.6 mmHg

Elementary analysis: Found: C 81.5; H 8.8%. Theoretical (as C₁₁ H₁₄ O):C 81.4; H 8.7%.

Ir (liquid film cm⁻¹) 3140(═C--H), 2800, 2700(CHO), 1720(C═O),1610(C═C), 800, 740.

Pmr (ccl₄ solvent, TMS internal standard, δ) 9.52(CHO, 1H),5.5(--CH═CH--, 2H, complex multiplet) 3.40-0.95(11H, complex multiplet)

¹³ CNMR (CDCl₃ solvent, TMS internal standard) 22.2, 25.9, 32.2, 32.4,38.6, 38.9, 39.4, 40.5, 41.3, 42.2, 42.5, 47.5, 50.5, 52.6, 53.0, 130.4131.8, 132.2, 132.5, 203.2, 203.8.

MS, M/E (relative intensity) 162(21), 96(21), 95(31), 91(31), 79(25),77(24), 67(93), 66(100), 41(27), 39(36).

The starting mixture of 8- and 9-formyl-endo-tricyclo [5.2.1.0²,6 ]deca-3-enes (Formula II) can be prepared as described in the applicationof Yoshiaki Inamoto, Yoshiaki Fujikura and Hiroshi Ikeda entitled "8-and 9-Exo-Formyl-Endo-Tricyclo [5.2.1.0²,6 ] Deca-3-Enes," Ser. No.744,955, filed Nov. 26, 1976, now abandoned corresponding to JapaneseSer. No. 144675, filed Dec. 4, 1975). The formula I compound can betransformed to the formula II compound tricyclo [5.3.1.0³,8 ] undecane,a known useful compound, as described in an application of YoshiakiInamoto, Yoshiaki Fujikura, Kiyoshi Tsuchihashi and Eiji Kashiharaentitled "Process for Hydride Transfer Reduction Rearrangement of8-Exo-Hydroxymethyl-Endo-Tricyclo [5.2.1.0²,6 ] Decane" Ser. No.744,957, filed Nov. 26, 1976, now U.S. Pat. No. 4,059,643, correspondingto Japanese Ser. No. 144673/75, filed Dec. 4, 1975). The entire contentsof these two applications are incorporated herein by reference.

The embodiments of the invention in which an exclusive property orprivilege is claimed are defined as follows: 1.8-exo-hydroxymethyl-endo-tricyclo [5.2.1.0²,6 ] decane.